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U Fen. 9, 1932. H. s. DAVIS ET AL PROCESS FOR GENERATING TERTIARY AMYL ALCOHOL Original Filed Feb. 24, 1925 Patented Feb. 9, 1932 UNITED STATES PATENT 4OFFICE:-

HABOLD S.V DAVIS, OF BELMONT, AND WALLACE MURRAY, OF READING,` MASSACHU-- SETTS, ASSIGNOBS, BY MESNE ASSIGNMENTS, TO PETROLEUM CHEMICAL CORPORA- TON, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE IPROCESS FOR GENEBATING TERTIARY AMYL ALCOHOL v Original application led February 24, 1925, Serial N q. 10,992, and in Germany February 23, 1926. Divided and thisl application fled March 28,' 1930. Serial No. 439,653.

This application is- .a division of parent application, Serial No. 10,992, filed February 24, 1925.

This invention relates to the preparation,

5 segregation and utilization of oleiine hydrocarbons and to the v`production of their hydrocarbons, olefines are capable of readily reacting or combining With reagents, including the polybasic acids (of which sulphuric acid or phosphoric acid are typical) the halogens and halogen compounds, hypochlorous and other acids.

rllhe reaction of sulphuric acid with the oleines has been known since its discovery .in Faradays laboratory in 1826, and alcohols have been prepared from alkyl sulphuric acid roducts of this reaction on certain olenes y hydrolysis and distillation by numerous investigators since Berthelots research in 1863. Derivatives of olenes have been made on a commercial scale in this country by rst preparing an acid reactive liquor of sulphuric acid with oil gas since as early as 1906 (American Ether Company Chemie, 1896, pp; 456,- 459, Die Chemische Industrie, vol. 35, p.' 637, 1912). Gases produced in the liquid phase 40 cracking of petroleum have been similarly treated `for the recovery of alcoholic mixtures including isopropyl, secondary butyl and amyl alcohols. These treatments, so far as We are aware, have been of a, kind adapted to i5 the incidental recovery at gas works or petroleum pressure stills of gases from cracking i operations rarely containing more than 12% of olenes, and free from any substantial contents of very reactive highly cracked hydroacid of a degree of concentration selected to reach a result necessarily in the nature of a compromise between destruction by polymerizatlon or otherwlse of the more reactive .olenes, and incomplete sulphation; and

hence, with partial recovery only of the realizable voleiue values and with high acid consumption. Such processes are economically justiiiable'only whenlean gases are available in great quantities otherwise Wasted. They are not so justifiable When the gas to be treated is rich in olefines so reactive as to be converted into polymers .While making the oleiine-acid compound of a less reactive remainder When the olefine bearing gas is rich in highly reactive oleines,asingle-stage treatment to obtain acid products cannot be practised; the reaction ofthe more highly reactive olelines and other hydrocarbonsto polymer under treatment With acids capable of forming addition compounds With the less reactive olenes is too vigorous and too productive of heat topermit this even in the case of relatively lean gases. v

The known procedure has therefore been to destroy the very reactable olenes in one lot of acid, and sulphate the remainder in another l'ot of acid. y 35 lf vit were practicable to obtain mixed alkyl acid compounds and other derivatives ofthe rich gases, such as result from vapor hase cracking directed to the production o oleiines, by a group reaction with acid, the result so would not be desirable. The different alcohols, at least eight in number, resultin from hydrolysis of the obtainable compoun s have boiling points ranging from 80 to 140 C., and separation from each other is in most cases not feasible. The uses of these alcohols (e. g. isopropyl and amyl alcohols) are widely A divergent, and to produce them in admixture would be commercially undesirable.

This process provides a treatment of olefine hydrocarbons, liquid or gaseous, particularly mixed hydrocarbons resulting from as complete generation of these substances as possible from a suitable hydrocarbon material or carboniferous material of the classes above enumerated, and therefore occurring richly in the material presented for treatment, and containing the very reactive highly A' cracked hydrocarbons such as the diolenes, isobutylene, trimethylethylene, unsymmetrical methylethyl-ethylene and other unsaturated bodies having a high reactive affinity for combining acids or other reactants, and also containing other olefines of a lower order of reactivity toward the said combining agents; for example, propylene, isopropyl,

ethylene,\butene1,.butene-Z, pentene-l and pentene-2. This new process thus provides a mode of treatment applicable to hydrocarbon products rich in highly reactive or unsaturated olefines to recover valuable derivatives and segregate the voleiine substances in the order of their chemical activities toward reagent substances, for example polybasic acids; and which will permit the separation production,

c severally or in groups, of olefine compounds,

such as the olefine-acid compounds capable of hydrolysis or other after-treatment and separation, leading to separate production of the consequent dilferent alcohols or other oleine derivatives. An object attained by the process is the separation of complex olefine mixtures, especially mixtures rich in olelines,

of the several fractions at the respective sltagel of the operations..

The process conserves for use at a further stage of the process such of the reactive olefines as are not concerned at any stage of the process in the reaction contrived and intended to produce a particular derivative or intermediate. 'I `he recommended procedure comprises a stage or stages of separation of a fractionor fractions of the material containing the olene or olene groups to be recovered, followed by treatment selectively to differentiate and segregate the component oleine substances in accordance with their` respective and relative chemical reactivities. In general it may be stated that the preferred raw material contains more than 30% of unsaturated hydrocarbons.

It is advantageous,`in'th'e practice of. this process, to proceed upon a basis of known contents of the raw material, and for this purpose a preferred raw material for the process is-petroleum, treated by any process of vapor phase cracking tending to produce aproduct rich in oleines and preferably substantially free from normally liquid paraffine derivatives. raw material is the constant and controllable mixture produced by the process described in the application for Letters Patent by Earl P. Stevenson and Clarence K. Reiman, Serial No. 8,907, filed February 13, 1925, which comprises subjecting vapors of a petroleum or a fractional distillate of petroleum, for example gas oil, so called, to heat during flow in a tubular retort heated at successive zones thereofto differing degrees, with the effect of maintaining the vapors at a nearly Iconstant cracking temperature during a substantial time of flow, this constant temperature being such as to result infoptimum development of olefine values.r For this purpose, a cracking temperature maintained nearly constant at a selected value between 60000. and 650o C. during a suiiicient time A suitable and preferred of flow to produce from 1000 to 1700 cubic feet of gaseous product per barrel of 42 gallons passed produces satisfactory vmaterial for this treatment. The preferred vapor-phase cracking temperatures are higher than those heretofore known for the commercial production of motor spirit, which do not exceed 500 C., so far as I am aware (Lewes, Journal Society of Chemical Industry, Vol. XI, page 585) and are not such high temperatures (700o to 1000o C.) as are used for making oil gas b the known methods of Pintsch, Fritsche or llman. i

The invention will therefore now be described as carried out upon the gaseous efilux ofl vapor phase cracking of petroleum so contrived as to produce a vaporous and gaseous efflux which, when stripped of a motor spirit fraction, is exceedingly rich in the olefine substances above mentioned. But it will be understood that this process is applicable without change, except in degree, to the treatment of other complex olefine mixtures, and that the specific instances now-to be described are described byway of illustration of the invention, and are not to be viewed as comprising every instance of practice according to the invention.

In the accompanying'drawing, the figure is a diagrammatic flow sheet showing appreferred assemblage of apparatus illustrative of certain physical stages of separation -of the material treated. 'Y

The process to he described comprises, 1n general, submitting the oletine-bearing gases to treatment for the physical separation of fractions containing groups'ofl oleine substances capable of chemical segregation con- 'secondary vaporizer 6, which may be substantially the same kind of tubular heater as the primary preheater 4. Between theV preheater 4 and superheater 6 the flowing stream, already substantially all vapor, `may be subjected'to treatment adapted to separate out the inclusions of low volatility, and pass on the vapors and gases. A liquid separator 5, preferably of a kind operating without substantial loss of heat,I is recommended. Collected liquids 'from this separator may dow through a pipe 6x1 and a cooler C to tar storage tank 10.

Vapors superheated at 6 pass to a cracking tube 7. The eliluent gases, vapors and suspensions from cracking are recommended to be. treated in a separator 8, which may work on the Cyclonic or centrifugal principle, and deliver'its' liquid separates into the pipe 6, and its vaporousand gaseous elux into the bottom of the rst of a series of separating and condensing towers, for example, the tower 11, adapted to counter-current iiow in contact of the vapors and 'gases and the condensate from tower 12, which in turn .is adapted to counter-current flow` of the vapors and gases and the condensate from a fractionating condenser 13 of any suitable reflux type.

The tower 12 is preferably a fractionating tower of the bubble type. From the bottom is taken a relatively heavy fraction which is delivered into the top of tower 11, wherein it serves to condense and wash out any heavy and undesirable 'tars formed in the cracking reaction. F rom one of the'lower plates of this tower is drawn off a fraction of substantia lly the same boiling range as the feed stock,- but as this will, of necessity, contain some hydrocarbons in the motor spirit range, it cannot be returned to the feed stock without materially decreasing the yield of motor spirit. Provision is included, therefore, for stripping this fraction of its lighter hydrocarbons, such as-a fractionatingtowcr 12a, which is heated at thebase at 1.4 and delivers overhead the desired fraction of its feed into-one of the top plates of tower 12. The stripped cycle stock is delivered through a tion rich in propylene and ethylene, and hereinafter referred to as apropylene fraction.

For example, the gaseous effluent from condenser 18 `may bedelivered through meter M andV scrubbed in absorption towers 20 and 21 by a counter-current flow of cool absorption oil stored in a tank 23 delivered by a pump P1 through a cooler d2, through pipe 24 to the absorption tower 21 and thence through a cooler C3 to the top of tower 20, and the saturated oil delivered through a pipe 26 to a storage tank 27, whence the saturated oil 'may flow through a heat exchanger 28, pipe still 29 and vaporizer 30 to a redux ing tower 31, from which the liquids may be led through cooler C4 to the crudecmotorfspirit or gasoline storage tank 16 by pipe 32.

Unvaporizedabsorption oil from vaporizer 30 may flow through pipe 30B, heat eX- l changer 28, and cooler C5 to tank 23.

The vaporous euent at 33 may be deliveredthrough a condenser 34 anda separator 35, whence the vapors pass toa compressor 36 and pressure storage tank 37. Condcnsates at 34, 35 and 37 `may be delivered to tank 17, the pressure and temperatures being such as to provide at these points liquid fractions corresponding -to the amylene-fraction fluid in tanl 17. Pressure tank 37 may deliver, if desir( d, through a suitable reduction valve 39 to gas-holder 40, in which are collected the residual gases from the saturatedscrubbing oil. This gaseous fraction, if so separated, represents substantially the major portion of the butylene hydrocarbons, whereas the residual gas from tower'21, collected in the holder 22, contains the propylene and ethylene.

' When appropriate conditions are realized in and prior to flow through the cracking tube 7, the respective fractions capable of being separated' by steps of condensation or ab-` sorption are sharply characterized by the desired preponderance (amount under -good conditions to substantial feedom from :mix-

sought tol be collected and separated. Any

- suitable condensation or absorption fractionatingtreatment may therefore be resorted to, and the apparatus mentioned may be varied v in accordance with engineeringl preferences. Under preferred conditions, cracking in the tubev 7 :is at a relatively constant temperature at orV about 600 C. to 615 C.

The following typical exam le of operation of the vapor phase crac ing process Results of 3ft-hour run (quantities per bbl.)

. throughout Gas oil used, 31 Baum Crude motouspirit recovered-- 74.5 lbs. Cycle stock 110 lbs. Fuel oil 30 lbs. Process gas at M (rich gas) lbs. (1040 cu. ft.)

. Residual gas from compresL sion to 250 pounds per sq. -1 f n 33.4 lbs. (533 cu. ft.) Pressure condensate 40.61 lbs.

Products for pressure comleusate Amylene fraction (liquid).

u to 25 C 4.51lbs. (b) 25 to 45 C 5.15 lbs. Butylene fraction-(gaseous) 19.6 lbs. (181 cu. ft.)

Light naphtha (included in 2) 11.35 lbs.

. These results are from separation by compression,

distillation and condensation When the absorption step, as described above, is resorted to, typical results are as follows:

Feed stock.32-34 B. gas oil (from South Texas crude).

Feed rate-1 bbl. per hour per six inch cracking tube.

Ll'empcralurcs- Vaporizer 632 C. maximum Tube 601 C. (average) Tube sections .(amerages) Entrance 2 3 4 595 C. 602 C. 602 C. 603. C.

Conversions per bbl. passed- Process gas (Sp. Gr. 1.055) .1035 cu. ft. Oil scrubbed gas (Sp. Gr. 0.929) 675 cu. ft. Butylene fraction (non-condensed gas from distillation of saturated absorp- 5 e 006 c. v603" c.

Vapor phase cracking of the preferred practice having been carried on at Vthe 'temperature mentioned, the products are chiefly unsaturated, being largely olefines with some naphthenes and aromatichydrocarbons, to-

gether with almost negligible amounts of saturated or parain hydrocarbons, particularly in the lighter liquid fractions. The oleine content of the gas prior to compressing or .oil scrubbing to remove condensibles may be as-high as 54% by volume inthe operation of an appropriate vapor phase crack-r ing process, for example that described. 'For comparison, the'olefine content of pressurestill gases is seldom higher than 10%, and is usually under I8%, justifying designation as lean gases.

The aggregate chemical character of these 'two classes of olene mixtures is likewise quite different, so that steps for the recovery of derivatives applicable to the lean gases are not applicable to the richer mixtures, The olefines in pressure-still gases have a high proportion of normal olefines, and do not contain substantial amounts of the very reactive, highly cracked hydrocarbons, such as the dioleiines.

The recommended steps above described,

for which other procedures may of course be substituted within the invention so long as the resultsare produced, result in a fractionation of the oleines as follows:

Boiling 'points= Ethylene' 103 C.

Gaseous Propylene 48.4 C.

bt Iso-butyiene 6 C. Butylene Butene-l 5 C. Butene-2 +1 C.

. 'Boiling fcioints: isopropyl ethy1enc 21 Un sym. methyl-etllyleth lene 31-33 C..

Li uid Amylens Penteiie-zl 36 q 'rrimethyl @thyme 37 to 42 c. Pcntene-1 39 to 40 C. Hexylenes 55 vto 75 C. Higher Olenes, up to 150 C.

Associated with .the amylenes and butylenes are substantial inclusions of dioleiines, believed to be butadiene, isoprene, and their homologues.

We are aware of no practical arrangement of conditions or procession of reagent sub stances by which any Whole mixture of these gaseous substances can be treated to yield in succession the derivatives of the unsaturated hydrocarbons present in theml in amounts constituting valuable sources of'materials needed for industrial uses. But, we have nevertheless determined that the substances are reactivewith the polybasic acids, for .example sulphuric acid, in a certain order, ethylenevbeing the least reactive as follows:

-m ci mgsosgog-l Boiling points -State Ethylene cH :ou: 103. c. lGsm Propylene c.-cH=cH2 y 48.5 c. Gas gengive- (ga-(Cz-(lz-gl=gls2 39 4 Eeuw en ene- 36 C. 741 uid nume-1 cH-CH-CH.=CH2 5 mm) Gils orin solution Butene-2 CH3-CH=CH1CH3 1 C. GHS 01 in S0- Isopropyl ethylene CHS lution HCH=CH2 21 C. Liquid CH 8. Unsymmetrical methyl ethyl ethylene CH, C=CH= 31 to 33 C. Liquid CHa'r-CH s. Trimetnyl etnynnecn CH y =o 37 to 42 C. Liquid y Y 0H n 10. Iso-butylene C C=CH2 6 C. Gas or in s0- C lutlon To absorb ethylene and produce ethyl sulphuric acid it is necessary to use hot concentrated acid which will substantially polymerize all other olefines above `prop lene in reactivity; the propylene will also e polymerized.

`With 100% acid below 30 C., there is no Y appreciable absorption of ethylene and the absorption of propylene is very rapid, but the yield of isopropyl alcohol will be small due to the excessive polymerization when and if the gas treated contains the more reactive oleiines in the amounts in which they naturally occur.

The following causes may be responsible for this phenomenon:

(l) The reactive oleines evolve so much heat on contact with the sulphuric acid that local overheating occurs which tends to polymerize all the dissolved products including propylene. y

(2) The reactive oleiines combine with the sulphuric acid more rapidly than propylene and decrease the ability of the acid to absorb the latter.

(3) 100% sulphuric acid can easily act as an oxidizing agent toward the reactive olenes and the water evolved dilutes the acid and lowers its power to absorb olenes.

Per contra, if the gas is treated with acid of a strength adapted toabsorb trimethyl ethylene and of the proper strength and under the optimum conditions to absorb Y.the olefines which yield tertiary derivatives (Nos. 8, 9, l0 above) there is no substantial absorption of the lighter and, simpler olefines such as propylene. For a quantitativeidea of the great variations in reactivity manifested by these oleiines towards sulphuric acid, isobutylene is several hundred thousand times as reactive as ethylene.

In the case of'isopropyl ethylene, which so far as we are aware has never, previous to the research leading to'this invention, lbeen converted-vinto an alcohol through reaction with sulphuric acid, acids of sucient strength to absorb pentene-l and Fpentene-2 vquantitatively polymerize isopropyl ethylene at temperatures below-30 C-. Higher temperatures and more concentrated acid than this are required to absorb the other' olenes for the results desired, and the conditions for securing a good yield ofamyl alcohol from this particular oleine substantially polymer.-v

ize the other oletines except ethylene and propylene present in this mixed gas.

By the fractionating procedure above described we have avoided any necessity to subject to sulphuric acid absorption all of the reactive oleines at once, and any necessity for producing alcohols incapable of being subsequently separated. j

By processes extending and developing the results of this invention, some of which are the work of others and no part of this inven-v tion, at least eight different alcohols Amay be I produced from vapor-phase cracked hydrocarbons, having a boiling range extending from 80 to 140 C. v l

Ifthese were produced conjointly it would be impractical subsequently to separate them, and as the uses (of isopropyland amyl alcohols, for example) are widely divergent, such a mixture would be of little or'no commercial value. As a. specific example of this diiiculty two pairs of alcohols that cannot be separated by fractional distillation are 150813122511 alcohol (constant boiling mixture) boilingpoint Tertiarycliutyl alcohol-boiling point 79.92 C.

Tertiary amyl alcoholboiling ran e 101.6 to 102 C. Secondary butyl alcoholboiling po nt 99.5 C.

The processing of the total oleiines present in a cracked petroleum product to secure tertiary as well as secondary derivatives calls for a further departure from the art as practiced where tertiary derivatives. are not recovered. The usual procedure is to moderately dilute the product from sulphuric acid absorption with Water and then distill. The point to which this dilution must be carried to avoid destruction by the action of the sulhazard in distilling from 25% acid solution. e

Tertiary alcohols, however, behave quite dit erently and tertiary amyl alcohol, `for example, cannot safely be distilled from even a one per cent solution without substantial decomposition. The preferred procedure for recovering tertiary alcohols from admixture with sulphuric acid is to neutralize as with lime and distill from a neutral solution. It will be obvious that this procedure is not practical when applied to a complex sulphuric acid product containing small percentages of tertiary bodies as compared to secondary bodies. It becomes practical and feasible when the tertiary bodies are concentrated and segregated as in the practice of this invention.

rlhe procedure above described, to avoid the ditiiculties and provide the advantages just adverted to, separates the material into groups capable of being reacted upon preferentially in respect to their constituent members, Ythus enabling separations of the acid combinations with the constituent members of these groups severally. So far as there is advantage in separating them, these groups are:

('1) The gaseous fraction containing ethylene and propylene.

(2) The butylene fraction containing isobntene and butene-l or butene-2 or both of the initial low-boiling distillate fraction, and

(3) Theresidue of the condensate which' may contain each of the five -isomeric amylenes, with varying amounts of hexylenes and higher oleines.

Fraction (l) may now beit-,rented in l l.

ance with the specific relative properties of its constituents. Because this fraction will contain traces of dioletines and oletines more reactive than propylene, owing to the practical and obvious limitation of any system for physical fractionation, it is desirable to treat this fraction first with sulphurlc acid, by tower scrubbing, of a strength that will selectively react upon the ole-k ines (more reactive than propylene) therein present. In the preferred procedure this fraction is first scrubbed with acid of S50-84% strength and is then subjected to the action of sulphuric acid having a concentration from 95 to 100% at a temperature preferably below C., whereupon propylene is substantially absorbed. The ethylene remains relatively unaffected and maybe preserved and used in the gaseous condition, or subsequently be reacted upon, as for example by 'absorption in hot sulphuric acid resulting in the formation of ethyl sulphuric acid; or treated in any known way to produce ether. Specific and preferred modes of treating fraction (1) for the recovery of these values form no part of the present invention. y

Gaseous products belong to other series of hydrocarbons which may be present in minor quantities as impurities, either remain in the gaseous state, as in the' case o f methane or ethane, or remain unabso'rbed by the acid treatments; or, as in the case of acetylenes,

small.

Upon hydrolysis of the acid compounds severally obtained as described, under suitable conditions, as by the addition of water or steam, and distilling at corresponding temperatures, ethyl and isopropyl alcohols respectively may be recovered in the distillation, leaving a residue of substantially alcobol-free sulphuric acid.

The butylene fraction (2) capable of economic use contains butylenes difficult to separate from each other by distillation. Ofthese butene-l and butene-Q are less reactive chemically than iso-butylene. Derivatives of butene-l and butene-Z as a consequence of the intramolecular structure of these substances have a secondary molecular formation, whereas derivatives of iso-butylene have a tertiary structure. This may flow from the structure of iso-butylene, conceived as a central carbon bond being a double bond. 'As for example,

the addition of water (H2O) produces a tertiary alcohol having the structure:

CH; CH3 y CH| C CH Preferred procedures therefore comprise reacting upon the butylene fraction in the order of reactivity of these component substances, to form in several succession tertiary and secondary derivatives.

For example, the butylene fraction containing isobutene, butene-l and butene-Q all gaseous) is passed through sulphuric acid of a concentration of 60% more or less in such manner as to effect as intimate a contact between the gas and the acid as possible, for the purpose of absorbing isobutene. Recommended apparatus comprises an interrupted lHow tower with glass or other inert packing arranged for counter-current flow of gas and satisfactory differential absorption is practicable at all ordinary temperatures. The isobutene is here selectively absorbed, leavmg the butene-l and butene-Q and other gases, if any, which are then conducted through sulphuric acid of a cnc'entration of 80%, more or less, by which the butene-l and butene-2 are substantially absorbed. One of the` advantages of this procedure' arises from having removed the substances reacting to tertiary compounds, since the reaction of the secondary-alcohol -forming substances with stronger acid for their conversion evolves heat of lesser degree, and the. natural rise of temperatures, for example to 40 C., may be permitted to take place, unless acid more concentrated than 80% is resorted to, in which case it maybe desirable to hold the temperature down to a point below 15 C. These .reactions are preferably carried out in a tower similar to the tower j ust mentioned; one tower may be used'if arrangement is made to collectthe gaseous efflux and repass it supplying the more concentrated acid on the second passageand separately collecting the liquid eiux from the first and the second passage.

' The liquid from the first of said steps contains the isobutene either absorbed in the acid or in theJ form of tertiary butyl alcohol by auto-hydrolysis in the dilute acid: this may be further diluted for complete hydrolysis and the alcohol distilled'therefrom. Preferably the dilute liquid is neutralized with an alkali before distillation. to result in a niueh higher yield of the tertiary butyl alcohol by acid. Isobutcne is very highly reactive: a

avoidance of reaction withthe acidduring obtain a high yield of secondary butyl alcohol. The distillate may be dehydrated, if desired, Vby any usual lor customary waterabsorbent chemical treatment, such as treatment with lime or caustic.

The amylene `fraction (3) whether' collected by absorption as described or by pressure condensation and fractional distillation of fraction (l) (propylene, cthylenepetc.) consists preponderantly of the amylenes and may contain hexylenes and higher olefines as well as hydrocarbons of the group Cul-12H. This liquid mixture, which typically colftains less than 5% of parans, may advan'- tageously be distilled into three parts corresponding to temperatures (a) up to 25 C. (b) 25 to 45 C. (c) above 45 C.

Since the lower or more volatile olefines have been substantially removed as above described, distillate (a) consists primarily of isopropyl ethylene, distillate (b) of politenetitiesof isopropyl ethylene. The specific treatment of this ldistillate forms no part of our invention herein claimed.

In order to secure substantial yields of alll alcohols derivative from the mixed amylenes of fraction (b) it is desirable to remove the hydrocarbons of the group CH2 2 (and any still less saturated hydrocarbons) which may be present. Either of the alternative processes is satisfactory at this stage.

It has been found, for example, that by treating this fraction first with concentrated hydrochloric acid, the amylenes which are convertible into tertiary derivatives are substantially converted into chlorides which, owing to their relatively high boiling points, can be easily separated from the unchanged amylenes. The resulting mixture of chlorides on hydrolysis, carried on preferably with the addition of lime or caustic soda, yields tertiary alcohols.

We do not herein claim the specific method of recoverv with the aid of hydrochloric acid treatment.

Alternatively the amylene fraction (3) of the olefine gases may be treated with sulphuric acid having a concentration of more or less, which promotes the formation of tertiary alcohols by bringing about the addition of water to isobutene, trimethyl, ethylene, unsymmetrical methyl-ethyl-cthylene and 4'probably some of the higher oleines While concurrently effecting the polymerization of or sulphuric acid treatments, a highly refined amylene fraction remains after treatment, which fraction is substantially a mixture of isopropyl ethylene, pentene-l and pentene-2, and which does not contain appreciable amounts of the other olefines,

`though there is no disadvantage in the presenceof substantial. amounts of the normal butylenes and hexylenes at this stage, since these olenes areof the same order of activity as'the amylenes therein present, and their derivatives can easily be separated from those of the amylenes by fractional distillation.

Addition of sulphuric acid of a concen` tration of 77% more or less tovthis refined amylene causes absorption with concurrent. formation oftthe corresponding inter1rned-l ates of the alcohols from which the corrosponding alcohols may be recovered by dilution and distillation.`

To further illustrate the advantage of this invention we have treated the rich gas from vapor phase cracking as described, without first removing the amylene fraction, with 95% acid. The result was an ,evolution of excessive heat, rendering control diflicult, if not impossible, and the recovery of small amounts only of secondary alcohols, and no tertiary alcohols. There were also formed large quantities of heavy tar-like polymers. By first removing the-oleines higher than propylene We have .successfully used fuming sulphuric acid as an absorbent for the remainder, obtained an alcohol yield of 40% I of theweight of acid used, and minimized the polymer formation to under 50% of the alcohol produced.

For specific examples 'of treatment of the amylene fraction 3,'(6) we have obtained the following results:

Example I continue this treatment over a period of 6 hours as a maximum, adding the acid in two equal portions :at` 3 hour intervals. 'At the ving the mixture preferably below 20 C., and

y or acid layer,

end of this period agitation is stopped and the mixture allowed to settle for a time sulicient to result in separation into two welldened layers. We first draw oii:I the lower which is carefully neutralized with caustic and distilled, preferably through a fractionating column, cutting when thel temperature reaches 100 C. at the up to 60o C. is segregated and treated for conversion into secondary alcohols.

Starting with 2.6 gallons of amylene frac.- tion, there is recovered 1.1 gallons of hydrocarbons boiling up to 60 C. which are now treated with 77% H2501, in two portions, each of .55 gallons or 7.65 lbs. In this stage the temperature is allowed to rise to C. and maintained at under C. preferably, and agitation is continued over a total period of six hours. The mixture is then allowed to settle and the lower or acid layer is drawn off, diluted with water tol bring the concentration of acid below 20%, and then distilled until practically all of thev alcohol is carried over. The distillate consists of two layers, a lower or water layer and an upper or alcohol layer. lFrom the 2.6 gallons of amylene fraction at the start of this processing, there is recovered under the above specific conditions .56 gallons of crude secondary alcohols.

Secondary and tertiary butyl'alcohols are successfully recovered from the `butylene fraction by first scrubbing with 65% more or less s ulphuric acid, and then with 77% more or less sulphuric acid, as above described.

Example II y Concurrently with the production of 2.6

gallons of amylene fraction there is recovered 102 cu. ft. of butylene fraction as set forth in the example above of a typical vapor phase cracking operation. VAs stated, this fraction can be absorbed under pressure or by cooling or both in the amylene fraction; or it can be -treated separately to produce tertiary and secondary butyl alcohols. The following is an example of separate treatment:

The butylene fraction is first scrubbed or,

treated with a relatively dilute sulphuric acid, followed by more concentrated acid. We have obtained satisfactory results by using the first absorption stage 65% vacid and in the second 77% acid. The amount of acid required depends upon the physical efficiency of the absorption apparatus employed in large measure; using even comparatively lneii' lons of secondary alcohols.

During the absorption of the butylene in the treatment for tertiaryI alcohol with the particular reagents mentioned above we prefer to keep the temperature below 20 C., and during the secondary stage at about 35 C.

As in the case of the tertiaryamyl alcohol, it

is necessary to d istill the tertiary butyl alcohol from a neutral or slightly alkaline solu'- tion to secure the highest yields, though tertiary butyl is not subject to decomposition in acidf distillation in the same degree as tertiary amylalcohol.

Wherever in this specification particular concentrations of acid reagent substances adaptedto oleiinev absorption are alluded to, it will be understood according to the common r,knowledge of the numerous chemists familiar with the behavior of acids toward olefines fornearly a century, that the acid concentration is relative to the respectively mentioned or to normal temperatures, and that at different temperatures another concentration of acid is equivalent, within those limits at which the action of the acid reagent ceases to become an absorption, and enters upon the destructive formation of the compounds herein alluded to as polymers.

For the operations of fractional treatment with HZSO4 e. g. of the amylene frac-tion (b) we recommend the use of apparatus comprising achambcr adapted to be heated or cooled,

and equipped for mechanical agitation of its contents; adapted for the slow feed of acid of the appropriate concentration; suit-v able settling vessels for decanting off vthe unchanged residue of the materials of lesser reactivity; and appropriate vessels for acid reaction upon the decanted residue. Distillation of the olefine-acid liquors may proceed lil) in appropriate steam' stills. In essentials,

the' units of apparatus required are familiar in the practice of the chemical industries, and one of the advantages of this invention resides in the relatively simple nature of the instruments and operations required.

We claim:

1. In the process of generating tertiary amyl alcohol from a mixture of hydrocarbons produced by cracking petroleum oil and containing both secondary and tertiary olefines, the steps of separating from said mixthe selective sulphation of tertiary oleines contained in said fraction is accomplished by contacting said fraction with aqueousv sulphuric acid of not exceeding '65%, HZSO., content.

3. Process according to claim 1, in'which the selective sulphation of tertiary Olefnes contained in said fraction is accomplished by contacting said fraction with aqueous sulphuric acid of not exceeding 65% H2804 content, at temperatures not exceeding 20 C.

4. In the recess of generating tertiary amyl alcohol rom a mixture of hydrocarbons produced by cracking petroleum oil and containing not less than 30% of unsaturated hydrocarbons including both secondary and tertiary olefines, the steps of separating from said mixture by distillation a fraction, the' olene content of which consists predominantly of secondary and tertiary oleiines of five carbon atoms to the molecule, and selectively sulphating the tertiary oleines contained in said fraction.

5. Process according to claim t, in which the selective sulphation of tertiary Oleines contained in said fraction is accomplished by contacting said fraction withaqueous sulphuric acid of not exceeding 65%, l-LSO@l content.

6. Process according to claim d, in which the selective sulphation of tertiary olenes contained in said fraction is accomplished by contacting said fraction with aqueous sulphuric acid of not exceeding 65%, H2SO4 content, Y at temperatures 20 C. 7. In the process of not exceeding generating ltertiary amyl alcohol-from a mixture of hydrocarbons produced by vapor phase cracking of petroleum oil and containing not less than 30% of unsaturated hydrocarbons including both secondary and tertiary oleines, the steps of separating from said mixture by distillationa fraction, the olene content of which consists predominantly of secondary and tertiary olenes of five carbon atoms to the molecule, and selectively sulphating the tertiary olenes'contained in said fraction.'

8. Process according to claim 7, in which the selective sulphation of tertiary oleines contained in said fraction is accomplished 'y contacting said fraction with aieous sulphuric acid of not exceeding 65%, 2504,

content.

9. vProcess according to claim 7 in which the selective sulphation oftertiary olenes "amyl alcohol from a mixture of Y bons produced by cracking petroleum oil and contained in V said fraction is accomplished by contacting said fraction with aqueous sulphuric acid ofnot exceeding H2304 ture by distillation a fraction, the olene content 'of which consists predominantly of secondary and tertiary olenes of live carbon atoms to the molecule, and selectively separating tertiary olenes from the said fraction. 11. In the recess of generating tertiary amyl alcohol fliiom a mixture of hydrocarbons produced by cracking petroleum oil and containing not less than 30% of unsaturated hydrocarbons including both secondary and tertiary olenes, said mixture by distillation a fraction, the olefine content of which consists predominantly of secondary and tertiaryroleines of five carbon atoms to the molecule, and selectively separating tertiary oleiines from the said fraction.

12. n the amyl alcohol produced by vapor phase cracking of petroleum Ioil and containing not less than 30% of unsaturated hydrocarbons including both secondary and tertiary olefines, the steps of process of generating tertiary separating from said mixture by distillation a fraction, the 4olefine content of which consists predominantl of secondary and tertiary olefines of five car on atoms to the molecule, and selectively separating tertiary olelines from the said'fraction.

HAROLD S. DAVIS. WALLACE J. MURRAY.

content at temperatlnes'not exceeding 20 C. a'

10. In the process of generatin ydrocarcontaining both secondary and tertia o le- 'flnes, the steps of separating from 'sal nux- V tertiary i from a mixture of hydrocarbons the steps of separating from 

